U.S. patent number 5,391,437 [Application Number 08/110,644] was granted by the patent office on 1995-02-21 for high-strength composite material and process for producing the same.
This patent grant is currently assigned to Nippon Kayaku Kabushiki Kaisha. Invention is credited to Akira Kajikawa, Masayuki Kiyomoto, Motokazu Mano, Takaaki Miyasaka, Hiroshi Sakurai.
United States Patent |
5,391,437 |
Miyasaka , et al. |
February 21, 1995 |
High-strength composite material and process for producing the
same
Abstract
A high-strength composite material obtained by kneading a
mixture comprising a non-hydraulic inorganic material, a
water-soluble polymer and water, molding the kneaded mixture,
drying the thus molded material and, optionally, treating the dried
molded material with an isocyanate compound, and a process for
producing a high-strength composite material which comprises the
steps of kneading a mixture comprising a non-hydraulic inorganic
material, a water-soluble polymer and water, molding the kneaded
mixture, and drying the thus molded material.
Inventors: |
Miyasaka; Takaaki
(Higashimurayama, JP), Kajikawa; Akira (Funabashi,
JP), Kiyomoto; Masayuki (Yono, JP),
Sakurai; Hiroshi (Iruma, JP), Mano; Motokazu
(Urawa, JP) |
Assignee: |
Nippon Kayaku Kabushiki Kaisha
(Tokyo, JP)
|
Family
ID: |
27315374 |
Appl.
No.: |
08/110,644 |
Filed: |
August 20, 1993 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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640418 |
Jan 11, 1991 |
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Foreign Application Priority Data
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May 22, 1989 [JP] |
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1-126644 |
Jul 17, 1989 [JP] |
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1-182526 |
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Current U.S.
Class: |
428/425.5;
427/337; 427/372.2; 427/385.5; 427/393.6; 428/423.1; 428/425.9;
428/688; 524/425; 524/430; 524/446 |
Current CPC
Class: |
C04B
26/02 (20130101); C04B 26/16 (20130101); Y10T
428/31609 (20150401); Y10T 428/31551 (20150401); Y10T
428/31598 (20150401) |
Current International
Class: |
C04B
26/02 (20060101); C04B 26/00 (20060101); C04B
26/16 (20060101); C04B 026/02 (); C04B
026/16 () |
Field of
Search: |
;428/329,330,331,423.1,424.4,425.5,425.9,688 ;524/425,430,446
;427/337,372.2,385.5,393.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0280971 |
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Sep 1988 |
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EP |
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48-78218 |
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Oct 1973 |
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JP |
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56-59655 |
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May 1981 |
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JP |
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60-15468 |
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Jan 1985 |
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JP |
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62-231704 |
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Oct 1987 |
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JP |
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63-282149 |
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Nov 1988 |
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JP |
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Other References
Chemical Abstract, vol. 93, No. 20, Columbus, Ohio, US Abstract No.
191077H, & JP-A-55 047 287 (Agency of Industrial Sciences and
Technology) Apr. 3, 1980..
|
Primary Examiner: Nakarani; D. S.
Attorney, Agent or Firm: Nields & Lemack
Parent Case Text
This application is a continuation of application Ser. No.
07/640,418, filed Jan. 11, 1991, now abandoned.
Claims
What is claimed is:
1. A composite material having a flexural strength of 244 to 1191
kgf/cm.sup.2 which is obtained by kneading a mixture comprising a
non-hydraulic inorganic material selected from the group consisting
of blast-furnace slag powder, silica fume, fly ash, silica sand,
silica rock powder, calcium carbonate, talc, clay, zeolite,
pearlite, diatomaceous earth, kaolin, alumina, titania and
zirconia, a water-soluble polymer and water, the water being
present in an amount of 5 to 30% by weight based on the
non-hydraulic inorganic material, molding the kneaded mixture, and
drying the thus molded material.
2. A high-strength composite material according to claim 1, wherein
the water-soluble polymer is a water-soluble polymer having the -OH
group.
3. A composite material according to claim 1, obtained by treating
the dried molded material with an isocyanate compound.
4. A process for producing a composite material having a flexural
strength of 244 to 1191 kgf/cm.sup.2 which comprises the steps of
kneading a mixture comprising a non-hydraulic inorganic material
selected from the group consisting of blast-furnace slag powder,
silica fume, fly ash, silica sand, silica rock powder, calcium
carbonate, talc, clay, zeolite, pearlite, diatomaceous earth,
kaolin, alumina, titania and zirconia, a water-soluble polymer and
water, the water being present in an amount of 5 to 30% by weight
based on the non-hydraulic inorganic material, molding the kneaded
mixture, and drying the thus molded material.
Description
TECHNICAL FIELD
The present invention relates to a high-strength composite material
comprising a non-hydraulic inorganic material as a main
constituent, and to a process for producing the same. More
particularly, the invention relates to a high-strength composite
material capable of being used as a building material, such as an
interior finishing material, a facing material, etc., and to a
process for producing the same.
BACKGROUND ART
Hydraulic inorganic materials, a representative of which is cement,
have long been used widely as structural materials and building
materials. However, hardened cement bodies are poor in flexural
strength, though they have high compressive strength, and many
attempts have been made to improve the poor flexural strength. For
instance, there have been known a method of using a water-reducing
agent to reduce the amount of water added, and a method of adding
silica fume or a blast-furnace slag powder so as to make the
structure of a hardened cement body denser, thereby seeking an
increased strength. Above all, Japanese Patent Publication No.
59-43431 (1984) discloses that, by making the addition amount of
water extremely small as compared with the conventional amount and
reducing the size of void and the porosity, it is possible to
increase the flexural strength of a hardened cement body to at
least 7 times the conventional value of 50 to 100 kgf/cm
.sup.2.
Besides, as a composite material using a non-hydraulic inorganic
material, e.g., calcium carbonate, instead of a hydraulic inorganic
material, e.g., cement, there has been known a resin concrete using
a urethane resin, polyfunctional acrylic resin or other similar
water-insoluble resin as a binder. The resin concrete has been
widely used as a floor material, a wall material or a material for
table counters.
The conventional resin concrete, using a non-hydraulic inorganic
material, often contains a cross-linking type resin as a binder
and, as a result, has a short pot life and is limited in kneading
and molding times. Accordingly, development of a hardened body
excellent in strength (especially, flexural strength) which uses a
non-hydraulic inorganic material and is substantially free of such
a pot-life problem is now desired.
DISCLOSURE OF THE INVENTION
The present inventors have made studies for solving the above
mentioned problems and, as a result of their studies, have
accomplished the present invention.
In a first aspect of the present invention, there is provided a
high-strength composite material obtained by kneading a mixture
comprising a non-hydraulic inorganic material, a water-soluble
polymer and water, molding the kneaded mixture, drying the thus
molded material.
In a second aspect of the present invention, there is provided a
process for producing a high-strength composite material which
comprises the steps of kneading a mixture comprising a
non-hydraulic inorganic material, a water-soluble polymer and
water, molding the kneaded mixture, and drying the thus molded
material.
In a third aspect of the present invention, there is provided a
high-strength composite material obtained by kneading a mixture
comprising a non-hydraulic inorganic material, a water-soluble
polymer and water molding the kneaded mixture, drying the thus
molded material, impregnating the dried molded material with an
isocyanate compound, and subjecting the impregnated material to a
heating treatment.
The present invention will be explained in detail below.
First, the non-hydraulic inorganic material in the present
invention is an inorganic material which is not hardened upon being
simply mixed with water. Examples of the non-hydraulic inorganic
material include a blast-furnace slag powder, silica fume, fly ash,
silica sand, silica rock powder, calcium carbonate, talc,
bentonite, clay, zeolite, pearlite, deatomaceous earth, kaolin,
alumina, titania, and zirconia. One or more of these materials may
be used either singly or in combination.
The water-soluble polymer usable in the present invention is not
particularly limited. However, it is preferable that the
water-soluble polymer is dissolved uniformly and rapidly in the
system being kneaded, within the keading time, and therefore is in
the form of fine particles. For instance, there can be used such
water-soluble polymers as follows: polyvinyl acetate derivatives
such as partially hydrolyzable polyvinyl acetate, cationized
polyvinyl alcohol, anionized polyvinyl alcohol, etc.; cellulose
derivatives such as hydroxypropylmethyl cellulose, hydroxyethyl
cellulose, carboxymethyl-cellulose, etc.; starch derivatives such
as soluble starch, cationized starch, etc.; polyethylene oxide; and
homo- and co-polymers prepared from the monomers mentioned below.
The monomers usable for preparing the homo- or co-polymers include
acrylamide monomers such as acrylamide, N,N-dimethylacrylamide,
N-isopropylacrylamide, acryloylmorpholine, etc.; (meth)acrylic
monomers such as tertiary amine salts of (meth)acrylic acid, sodium
(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, dimethyl- or diethyl-aminoethyl (meth)acrylate with
hydrochloric acid or sulfuric acid, quaternary ammonium salts which
are the Mens hutkin reaction products of dimethyl- or
diethyl-aminoethyl (meth)acrylate with methyl chloride, ethyl
chloride, benzyl chloride or dimethylsulfuric acid, etc.; vinyl
monomers such as N-vinylpyrrolidone, vinyl methyl ether, chloride,
benzyl chloride or dimethylsulfuric acid, etc.; vinyl monomers such
as N-vinylpyrrolidone, vinyl methyl ether, styrenesulfonic acid,
sodium styrenesulfonate, vinylpyridine or cationized derivatives
thereof, and so on. Particularly preferred water-soluble polymers
are water-soluble polymers having -OH groups, for instance,
polyvinyl acetate derivatives such as partially hydrolyzable
polyvinyl acetate, cationized polyvinyl alcohol, aninonized
polyvinyl alcohol. etc., hydroxypropylmethyl cellulose,
hydroxyethyl cellulose, homo- and co-polymers of 2-hydroxyethyl
(meth)acrylate or 2-hydroxypropyl (meth)acrylate.
The amount of the water-soluble polymer(s) used is preferably 1 to
15% by weight, particularly preferably 3 to 10% by weight, based on
the non-hydraulic inorganic material. If the amount of the
water-soluble polymer is less than 1% by weight, it is difficult to
knead the mixture or, even if it is possible to knead the mixture,
the resultant kneaded mixture tends to be brittle and to show poor
processability in the subsequent steps. Use of the water-soluble
polymer in an amount exceeding 15% by weight does not produce a
significant difference in the effects of the present invention and,
therefore, is disadvantageous on an economical basis; in addition,
such a large amount as this makes it more difficult to achieve the
improvement in water resistance, which is one of the effects of the
present invention.
The amount of water used varies depending on the kind of the
non-hydraulic inorganic material, the kind of the water-soluble
polymer and the amounts of these ingredients used. The amount of
water used should be so determined as to cause the resultant
mixture to exhibit good kneadability, and is generally 5 to 40% by
weight, preferably 7 to 30% by weight, based on the non-hydraulic
inorganic material.
In the present invention, an isocyanate compound may be used in
order to enhance the water resistance of the dried and hardened
material. Examples of the isocyanate compound include
monoisocyanate compounds such as phenyl isocyanate compounds, butyl
isocyanate, etc.; diisocyanate compounds such as
4,4'-diphenylmethane diisocyanate, tolylene diisocyanate,
hexamethylene diisocyanate, lysine diisocyanate,
trimethylhexamethylene diisocyanate, isophorone diisocyanate,
diisocyanate of hydrogenated 4,4'-diphenylmethane, etc.:
polyisocyanate compounds such as polymethylene polyphenylene
polyisocyanate, trimer of hexamethylene diisocyanate, isophorone
diisocyanate, etc.; reaction compounds of a di- or higher
polyisocyanate compound with a polyol, e.g., a reaction product of
hydrogenated bisphenol A (1 mole) with hexamethylene diisocyanate
(2 moles) or a reaction product of trimethylolpropane (1 mole) with
hexamethylene diisocyanate (3 moles), etc. Furthermore, blocked
type isocyanate compounds obtained by blocking a mono-, di- or
poly- isocyanate compound with phenol or the like and isocyanate
compounds obtained by carbodiimidizing part of the isocyanate
groups in a di- or poly-isocyanate compound, and the like can also
be mentioned. One or more of these isocyanate compounds may be used
either singly or in combination. Those isocyanate compounds which
have high viscosity or are solid are used in the state of being
diluted with or dissolved in a solvent (benzene, toluene, xylene,
etc.) unreactive to the isocyanate compounds. Preferable isocyanate
compounds are di- or higher polyisocyanate compounds.
The treatment with the isocyanate compound mentioned above gives a
favorable effect particularly when a polymer having hydroxyl groups
is selected as the water-soluble polymer.
Now, the process for producing a high-strength composite material
according to the present invention is explained below. In the
present invention, the non-hydraulic inorganic material, the
water-soluble polymer and water are roughly mixed with each other
by a mixer such as a paddle-type mixer and a planetary mixer. Next,
kneading is conducted, by using an apparatus capable of exerting a
strong shearing force on the roughly mixed material, for instance,
a roller kneader, a Banbury mixer, a wet-type pan mixer, a mixing
roll, a knett machine, a bag mill, a screw extruder, a
kneader-ruder, a pressure kneader, etc. This molding machine is not
particularly limited, and, in general, a calender roll, a low- or
high-pressure press, a (vacuum) extruding machine or the like is
used. Particularly when a method by which molding can be carried
out under a reduced pressure is used, for instance, when a vacuum
extruder is used, a hardened body having a high flexural strength
with little dispersion of flexural strength properties is obtained,
and such a method is preferable. The molding is followed by drying.
The present invention is characterized in that, unlike in the case
of using a hydraulic cement, a curing step is unnecessary and a
hardened body with high strength is obtainable by only drying. The
drying temperature is not specifically restricted, and is
ordinarily 60.degree. to 90.degree. C. Drying may be carried out at
normal temperature (10.degree. to 50.degree. C.) under a low
humidity of not more than 50% (relative humidity). When a method
comprising gradual drying (preliminary drying) carried out at
normal temperature followed by drying at a high temperature (e.g.,
80.degree. to 120.degree. C.) performed for 5 to 15 hours is
adopted, it is possible to reduce the strain induced in the
hardened body during the drying, and such a method is preferable.
The hardened body thus obtained is impregnated with an isocyanate
compound, if necessary.
As a method for the impregnation, a method of direct immersion of
the hardend body in the isocyanate compound or a method of
immersion of the hardened body in a solution of the isocyanate
compound in the above-mentioned organic solvent may be employed. A
method in which immersion of the dried and hardened body is carried
out under a reduced pressure to remove bubbles from the hardened
body while the isocyanate compound is permitted to penetrate into
the hardened body and, further, a method in which the just
mentioned treatment is followd by a pressurizing treatment to
accelerate the penetration of the isocyanate compound are also
usable. Moreover, a method of simply impregnating the hardened body
with the isocyanate compound under a reduced pressure or under
pressurization can also be used.
The impregnation can be performed satisfactorily at normal
temperature (10.degree. to 50.degree. C.), and the impregnation is
carried out for about 1 to 24 hours under normal pressure or for
about 1 to 24 hours under a reduced pressure or under
pressurization.
When the impregnating treatment is carried out by such a method as
mentioned above, the content of the isocyanate compound in the
dried and hardened body is generally 1 to 20%. The hardened body
impregnated with the isocyanate compound is then subjected to a
heat treatment. The heating temperature is preferably 60.degree. to
180.degree. C. The heating time, which depends on the heating
temperature, is generally 0.5 to 24 hours. The heat treatment may
be carried out in several steps at different temperatures.
The high-strength composite material of the present invention,
obtained in the manner as mentioned above, is characterized by a
high flexural strength and, in addition, extremely excellent water
resistance.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will now be explained more in detail while
referring to the following examples, which naturally should not be
construed as limitative of the present invention. The term "parts"
used in the following examples means "parts by weight".
EXAMPLE 1
One thousand (1000) parts of a blast-furnace slag powder
(Esment.RTM. -P, a product by NIPPON STEEL CHEMICAL CO., LTD.) and
100 parts of sodium polyacrylate (Panakayaku.RTM. -B, a product by
NIPPON KAYAKU K.K.) were placed in an Omni-mixer.RTM. (made by
CHIYODA GIKEN KOGYO K.K.) and were mixed. Then 190 parts of water
was added to the resultant mixture, followed again by mixing. The
thus obtained mixture was kneaded by a twin-roll kneader under a
high shearing force for 5 minutes. The kneaded material (dough),
which was clay-like, was extruded by a vacuum extruding machine
(Model HDE-2, a product by HONDA TEKKO K.K.) into a plate-like
shape (10 cm wide and 4 mm thick). The thus molded material was cut
by a knife to a 10 cm length, which was left to stand for one day
in a thermo-hygrostat at 30.degree. C. and 50% RH (preliminary
drying), and then dried for 8 hours in a hot-air dryer at
80.degree. C. Hardening was not observed during molding, and the
dough did not show a hardening phenomenon when left to stand for
one day, unless it was dried. The hardened body thus obtained was
cut by a diamond cutter to have a width of 1.5 cm and a length of 8
cm, thereby preparing a three-point bending test specimen. The
three-point bending test was carried out on a Tensilon (UTM2500, a
product by Orientec Corporation) under the conditions of a span
(interval) of 6 cm and a loading speed of 1 mm/min. The results are
shown in Table 1. The "specific gravity" refers to the specific
gravity of the hardened body (the same applied hereinbelow).
TABLE 1 ______________________________________ Bending modulus
Flexural strength of elasticity .times. kgf/cm.sup.2 10.sup.5
kgf/cm.sup.2 Specific gravity
______________________________________ 1191 3.27 2.17
______________________________________
EXAMPLE 2
The same procedure as in Example 1 was carried out, except that 100
parts of carboxymethyl cellulose (CMC-1160, a product by DAICEL
CHEMICAL INDUSTRIES, LTD.) as a water-soluble polymer and 230 parts
of water were used. The results are shown in Table 2.
TABLE 2 ______________________________________ Bending modulus
Flexural strength of elasticity .times. kgf/cm.sup.2 10.sup.5
kgf/cm.sup.2 Specific gravity
______________________________________ 496 1.16 1.93
______________________________________
EXAMPLES 3-12
One thousand (1000) parts of a blast-furnace slag powder
(Esment.RTM. -P, a product by NIPPON STEEL CHEMICAL CO.. LTD.) or
1000 parts of talc (Hitachi-Talc HT-300, a product by KUNIMINE
INDUSTRIES CO., LTD.), and a water-soluble polymer of the kind and
in the amount shown in Table 3 below were placed in an
Omni-mixer.RTM. (made by Chiyoda Giken Kogyo K.K.) and were mixed.
To the resultant mixture, water was added in the amount shown in
Table 3, followed again by mixing. The thus obtained mixture was
kneaded by a twin-roll kneader under a high shearing force for 5
minutes. The thus kneaded material (dough), which was clay-like,
was sandwiched between a pair of upper and lower sheets of
polyethylene terephthalate film, and was press molded under a
pressure of 30 kgf/cm.sup.2 to obtain a 4 mm thick plate-like
molded material. The dough was not hardened even when left to stand
for a long time. The molded material was left to stand for one day
in a thermo-hygrostat at 30.degree. C. and 50% RH (preliminary
drying), and was then dried for 8 hours in a hot-air dryer at
80.degree. C. The hardened body thus obtained was cut by a diamond
cutter to a width of 1.5 cm and a length of 8 cm, to prepare a
three-point bending test specimen. The three-point bending test was
carried out on a Tensilon (UTM-2500, a product by Orientec
Corporation) under the conditions of a span of 6 cm and a loading
speed of 1 mm/min. The results are shown in Table 3.
TABLE 3
__________________________________________________________________________
Non- Amount of Amount Bending hydraulic water-soluble of water
Flexural modulus of inorganic polymer used used strength elasticity
.times. Specific Example material (parts) (parts) kgf/cm.sup.2
10.sup.5 kgf/cm.sup.2 gravity
__________________________________________________________________________
3 Blast- Sodium 150 642 2.15 1.86 furnace Polyacrylate *1 slag 70 4
powder *6 Cationized 110 365 1.21 1.95 Polyacrylamide *2 70 5
Anionized 160 519 1.73 1.83 Polyacrylamide *3 70 6 Polyacrylamide
*4 150 442 2.07 1.85 50 7 Carboxymethyl 220 396 1.35 1.93 cellulose
*5 60 8 Talc *7 Sodium 160 514 1.70 1.88 Acrylamide 70 9 Cationized
140 264 1.19 2.00 Acrylamide 70 10 Anionized 140 311 1.60 1.97
Acrylamide 50 11 Polyacrylamide 180 493 2.29 1.87 100 12
Carboxymethyl 300 356 1.21 1.79 cellulose 70
__________________________________________________________________________
*1: Panakayaku .RTM.B, a product by NIPPON KAYAKU CO., LTD. *2:
Kayafloc .RTM. C566-2 (a copolymer of sulfate of dimethylaminoethyl
methacrylate with acrylamide), a product by NIPPON KAYAKU CO., LTD.
*3: Kayafloc .RTM. A275 (a copolymer of sodium acrylate with
acrylamide), a product by NIPPON KAYAKU CO., LTD. *4: Kayafloc
.RTM. N100 (a polyacrylamide), a product by NIPPON KAYAKU CO., LTD.
*5: CMC1160, a product by DAICEL CHEMICAL INDUSTRIES, LTD. *6:
Esment .RTM.P, a product by NIPPON STEEL CHEMICAL CO., LTD. *7:
HitachiTalc HT300, a prodcut by KUNIMINE INDUSTRIES CO., LTD.
EXAMPLES 13-23
High-strength composite materials according to the present
invention were obtained in the same manner as in Examples 3 to 12
except that 1000 parts of a non-hydraulic inorganic material of the
kind shown in Table 4 below, sodium polyacrylate or polyacrylamide
in the amount shown in Table 4 and water in the amount shown in
Table 4 were used.
TABLE 4
__________________________________________________________________________
Non- Amount of Amount Bending hydraulic water-soluble of water
Flexural modulus of inorganic polymer used used strength elasticity
.times. Specific Example material (parts) (parts) kgf/cm.sup.2
10.sup.5 kgf/cm.sup.2 gravity
__________________________________________________________________________
13 Talc *3 Sodium 60 150 480 1.76 1.89 14 Calcium polyacryl- 70 150
454 2.28 1.91 carbonate *4 amide *1 15 Silica 70 150 511 1.78 1.91
sand *5 16 Bentonite *6 70 300 482 1.07 1.92 17 Diatomaceous 70 250
255 0.82 1.50 earth *7 18 Clay *8 50 140 244 1.98 2.01 19 Blast-
Polyacryl- 40 140 422 2.18 1.98 furnace slag amide *2 20 Calcium 70
160 415 2.02 1.95 carbonate 21 Silica 70 160 348 1.55 1.74 sand 22
Bentonite 100 300 281 0.49 1.90 23 Clay 100 180 498 2.05 1.80
__________________________________________________________________________
*1: Panakayaku .RTM.B, a product by NIPPON KAYAKU CO., LTD. *2:
Kayafloc .RTM. N100 (a polyacrylamide), a product by NIPPON KAYAKU
CO., LTD. *3: HitachiTalc HT300, a product by KUNIMINE INDUSTRIES
CO., LTD. *4: White P70, a product by SHIRAISHI KOGYO KAISHA LTD.
*5: SR200, a product by KYORITSU CERAMIC MATERIALS CO., LTD. *6:
Kunigel .RTM. VA, a product by KUNIMINE INDUSTRIES CO., LTD. *7:
Oplite W3050, a product by HOKUSHU KEISODO K.K. *8: NK300, a
product by KUNIMINE INDUSTRIES CO., LTD.
EXAMPLES 24-27
One hundred (100) parts of talc [Hitachi-Talc HT-300, a product by
KUNIMINE INDUSTRIES CO., LTD.] and 7 parts of a partially
hydrolyzable polyvinyl acetate (KH-17S, a product by THE NIPPON
SYNTHETIC CHEMICAL INDUSTRY CO., LTD.) were placed in an
Omni-mixer.RTM. (made by CHIYODA GIKEN KOGYO K.K.) and were mixed.
Then, 16 parts of water was added to the resultant mixture,
followed again by mixing. The thus obtained mixture was kneaded by
a twin-roll kneader under a high shearing force for 5 minutes. The
kneaded material (dough), which was clay-like, was extruded by a
vacuum extruding machine (Model HDE-2, a product by HONDA Tekko
K.K.) into a plate-like shape (10 cm wide and 4 mm thick). The thus
molded material was cut by a knife to a 10 cm length, which was
left to stand for one day in a thermo-hygrostat at 30.degree. C.
and 50% RH, and then dried for 8 hours in a hot-air dryer at
80.degree. C. The hardened body thus obtained was cut by a diamond
cutter, to obtain a large number of samples having a width of 1.5
cm and a length of 8 cm. The samples were immersed respectively in
hexamethylene diisocyanate (HDI, a product by NIPPON POLYURETHANE
INDUSTRY CO., LTD.) [Example 24], tolylene diisocyanate
(Millionate.RTM. T-80, a product by NIPPON POLYURETHANE INDUSTRY
CO., LTD.) [Example 25], a polymethylene polyphenylene
polyisocyanate diluted with toluene to 50 (V/V)% (Millionate.RTM.
MR-200. a product by NIPPON POLYURETHANE INDUSTRY CO., LTD.)
[Example 26], a carbodiimide-modified isocyanate diluted with
toluene to 70 (V/V)% (Coronate.RTM. -MTL-C, a product by NIPPON
POLYURETHANE INDUSTRY CO., LTD.) [Example 27], in a vacuum chamber
at 15.degree. C. for 10 hours, and were then subjected to a heating
treatment in a constant-temperature dryer at 90.degree. C. for 20
hours. The samples thus obtained were found to contain about 3 to
15% of the isocyanate compound in the hardened body, by
determination of the change in weight of the smaple through the
impregnation. The samples thus obtained were immersed in water at
25.degree. C. for one day, and subjected to three-point bending
tests in a wet state. The three-point bending tests were carried
out also for the samples not immersed in water. The three-point
bending tests were carried out on a Tensilon (UTM-2500, a product
by Orientec Corporation) under the conditions of a span of 6 cm and
a loading speed of 1 mm/min. The results are shown in Table 5.
TABLE 5
__________________________________________________________________________
Properties after Properties before immersion in water immersion
water for one day Flexural Bending modulus Flexural Bending modulus
Isocyanate strength of elasticity .times. strength of elasticity
.times. Example compound kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
__________________________________________________________________________
Example 24 Hexamethylene 630 1.68 610 1.45 diisocyanate Example 25
Tolylene 650 1.90 350 1.22 diisocyanate Example 26 Polymethylene
610 1.65 480 1.32 polyphenylene polyisocyanate Example 27
Carbodiimide- 660 1.74 580 1.38 modified isocyanate
__________________________________________________________________________
EXAMPLES 28-32
The same procedure as in Examples 24 to 26 was repeated except that
a clay (NK-300, a product by KUNIMINE INDUSTRIES CO., LTD.) was
used as a non-hydraulic inorganic material, the amount of water was
changed to 15 parts, and that trimer of hexamethylene diisocyanate
diluted with toluene to 50 (V/V)% [Coronate.RTM. EH, a product by
NIPPON POLYURETHANE INDUSTRY CO., LTD.) and a reaction product of
hydrogenated bisphenol A (1 mole) with hexamethylene diisocyanate
(2 moles) diluted with toluene to 50 (V/V)% (Coronate.RTM. 2094, a
product by NIPPON POLYURETHANE INDUSTRY CO., LTD.) were added as
the isocyanate compound. The results are shown in Table 6.
TABLE 6
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Properties after Properties before immersion in water immersion
water for one day Flexural Bending modulus Flexural Bending modulus
Isocyanate strength of elasticity .times. strength of elasticity
.times. Example compound kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
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Example 28 Hexamethylene 700 1.95 680 1.64 diisocyanate Example 29
Tolylene 730 2.08 720 1.97 diisocyanate Example 30 Polymethylene
710 1.90 620 1.83 polyphenylene polyisocyanate Example 31 Trimer of
560 1.38 380 0.29 hexamethylene diisocyanate Example 32
Hydrogenated 540 1.21 320 0.22 bisphenol A & Hexamethylene
diisocyanate
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EXAMPLES 33-36
One hundred (100) parts of silica sand (SR-200, a product by
KYORITSU CERAMIC MATERIALS CO., LTD.) as a non-hydraulic inorganic
material and 5 parts of partially hydrolyzable polyvinyl acetate
(KH-17S, a product by NIPPON SYNTHETIC CHEMICAL INDUSTRY CO., LTD.)
were placed in Omni-mixer.RTM. and were mixed. To the resultant
mixture, 14 parts of water was added, followed again by mixing. The
mixture thus obtained was kneaded by a twin-roll kneader under a
high shearing force for 5 minutes. The kneaded mixture was
clay-like, which was sandwiched between a pair of upper and lower
sheets of polyethylene terephthalate film, and press-molded under a
pressure of 300 kgf/cm.sup.2 to obtain a plate-like shape 4 mm
thick. The molded material was subjected to drying and treatment
with an isocyanate compound, in the same manner as in Examples 24
to 27. The results are shown in Table 7.
TABLE 7
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Properties after Properties before immersion in water immersion
water for one day Flexural Bending modulus Flexural Bending modulus
Isocyanate strength of elasticity .times. strength of elasticity
.times. Example compound kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
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Example 33 Hexamethylene 570 1.31 550 1.22 diisocyanate Example 34
Tolylene 520 1.42 440 1.05 diisocyanate Example 35 Polymethylene
530 1.27 360 0.70 polyphenylene polyisocyanate Example 36
Carbodiimide- 550 1.28 480 1.18 modified isocyanate
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EXAMPLES 37-40
The same procedure as in Examples 33 to 36 was repeated except that
100 parts of a talc (Hitachi-Talc HT-300, a product by KUNIMINE
INDUSTRIES CO., LTD.) as a non-hydraulic inorganic material, 7
parts of a hydroxypropylmethyl cellulose (Marpolose.RTM. EMP-H, a
product by MATSUMOTO YUSMI-SEIYAKU CO., LTD.) as a water-soluble
polymer and 15 parts of water were used. The results are shown in
Table 8.
TABLE 8
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Properties after Properties before immersion in water immersion
water for one day Flexural Bending modulus Flexural Bending modulus
Isocyanate strength of elasticity .times. strength of elasticity
.times. Example compound kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
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Example 37 Hexamethylene 430 1.25 430 1.15 diisocyanate Example 38
Tolylene 400 1.33 340 1.03 diisocyanate Example 39 Polymethylene
440 1.41 430 1.28 polyphenylene polyisocyanate Example 40
Carbodiimide- 460 1.28 380 1.18 modified isocyanate
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EXAMPLES 41-44
The same procedure as in Examples 33 to 36 was repeated except that
8.5 parts of hydroxyethyl cellulose [HEC (SP-850), a product by
DAICEL CHEMICAL INDUSTRIES, LTD.] as a water-soluble polymer and 20
parts of water were used. The results are shown in Table 9.
TABLE 9
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Properties after Properties before immersion in water immersion
water for one day Flexural Bending modulus Flexural Bending modulus
Isocyanate strength of elasticity .times. strength of elasticity
.times. Example compound kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
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Example 41 Hexamethylene 500 1.54 500 1.58 diisocyanate Example 42
Tolylene 510 1.51 400 1.39 diisocyanate Example 43 Polymethylene
470 1.48 370 1.46 polyphenylene polyisocyanate Example 44
Carbodiimide- 490 1.55 410 1.32 modified isocyanate
__________________________________________________________________________
EXAMPLES 45-48
The same procedure as in Examples 33 to 36 was repeated except that
a blast-furnace slag powder (Esment.RTM. -P, a product by NIPPON
STEEL CHEMICAL CO., LTD.) was used as a non-hydraulic inorganic
material. The results are shown in Table 10.
TABLE 10
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Properties after Properties before immersion in water immersion
water for one day Flexural Bending modulus Flexural Bending modulus
Isocyanate strength of elasticity .times. strength of elasticity
.times. Example compound kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2
__________________________________________________________________________
Example 45 Hexamethylene 670 1.96 360 1.02 diisocyanate Example 46
Tolylene 630 1.75 290 0.98 diisocyanate Example 47 Polymethylene
690 1.86 300 0.88 polyphenylene polyisocyanate Example 48
Carbodiimide- 650 1.79 270 0.73 modified isocyanate
__________________________________________________________________________
EXAMPLE 49
The same procedure as in Example 26 was repeated except that 90
parts of a clay (NK-800, a product by KUNIMINE INDUSTRIES CO.,
LTD.) and 10 parts of silica fume were used as a non-hydraulic
inorganic material, and the heating treatment after impregnation
with the isocyanate compound was carried out at 80.degree. C. for 2
hours, at 120.degree. C. for 3 hours and at 150.degree. C. for 1
hour. The samples thus obtained were immersed in water for 1 day
and 7 days, respectively, and were subjected to three-point bending
test. The results are shown in Table 11.
TABLE 11
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Properties before Properties after immersion Properties after
immersion immersion water in water for one day in water for 7 days
Flexural Bending modulus Flexural Bending modulus Flexural Bending
modulus Isocyanate strength of elasticity .times. strength of
elasticity .times. strength of elasticity .times. Example compound
kgf/cm.sup.2 10.sup.5 kgf/cm.sup.2 kgf/cm.sup.2 10.sup.5
kgf/cm.sup.2 kgf/cm.sup.2 10.sup.5
__________________________________________________________________________
kgf/cm.sup.2 Example 45 Polymethylene 953 2.62 932 2.20 824 1.85
polyphenylene polyisocyanate
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INDUSTRIAL APPLICABILITY
The present invention provides a high-strength composite material
which is produced from a non-hydraulic inorganic material, is easy
to knead and to mold and has a high flexural strength after drying
and shows little lowering in the flexural strength even upon being
wetted with water.
* * * * *